CN110467178B - Method for preparing graphene - Google Patents
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- CN110467178B CN110467178B CN201910932814.1A CN201910932814A CN110467178B CN 110467178 B CN110467178 B CN 110467178B CN 201910932814 A CN201910932814 A CN 201910932814A CN 110467178 B CN110467178 B CN 110467178B
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Abstract
The invention relates to the technical field of graphene preparation, in particular to a method for preparing graphene, which is characterized in that expandable graphite is taken to be expanded in a graphite expansion furnace after being heated to 850-900 ℃ to obtain expanded graphite with gaps of 0.7-0.8nm, the expanded graphite contains functional groups containing hydroxyl and carboxyl with oxygen content of 2-3%, then the obtained expanded graphite is dispersed in a strong polar solvent to obtain a graphite interlayer compound, and a cavitation device is used for circulating and cavitating to obtain graphene slurry.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a method for preparing graphene, which has the advantages of simple steps, high production efficiency, low production cost, complete structure, no overlapping, no agglomeration and less defects.
Background
As is well known, graphene is a semi-metal material, in which carbon atoms are bonded by two-dimensional sp2 to form a single-atom layered structure of a hexagonal honeycomb lattice, has structural and chemical stability, and very excellent electrical, thermal and mechanical properties, and has potential application prospects in various fields such as energy, electronic materials, biomedicine and environmental protection.
Due to the numerous advantages and excellent properties of graphene, methods of mass production of graphene have been proposed and studied. In particular, a method capable of preparing graphene having less defects and having less thickness through a more simplified process has been variously studied so that excellent properties of graphene may be more remarkably expressed. The existing methods for preparing graphene mainly include: micro mechanical lift-off, redox, epitaxial growth, chemical vapor deposition, and the like. Micromechanical exfoliation is the simplest method, but only a very small number of graphenes are available. The redox method is a method which is applied more at present, and is mainly characterized in that graphene oxide is obtained by stripping graphite oxide and then reduced to obtain graphene, a large number of defects are introduced in the preparation process, the graphene oxide cannot be completely repaired during reduction, the performance and the application of the graphene oxide are seriously influenced, and meanwhile, the method is complex in production process, insufficient in yield and serious in environmental pollution. The epitaxial growth method and the chemical vapor deposition method can obtain high-quality graphene, but the two methods have harsh preparation conditions, low yield, high preparation cost, high energy consumption and serious environmental pollution. Therefore, there is a need to develop a preparation method of high-quality few-layer graphene, which is environment-friendly, low in cost, easy to operate, high in production efficiency and easy to realize large-scale production.
Chinese patent publication No. CN201811052075.9 discloses a method for preparing graphene by full-liquid water-phase physical stripping, which comprises the steps of soaking expandable graphite in water, then grinding the treated expandable graphite, then carrying out high-pressure homogenization treatment, emulsification treatment and ultrahigh-pressure critical treatment, standing for layering, and carrying out spray drying to obtain a graphene product. The method is green and environment-friendly, and the graphene lattice structure is complete. However, the method is difficult to obtain the graphene with small size and thickness, so that the large-scale application of the graphene is hindered, and meanwhile, the stripping yield and the productivity are insufficient, so that the method is not suitable for industrial production. Chinese patent publication No. 201611225104.8 discloses a method for continuously preparing graphene by using ultrasonic waves, which is mainly characterized in that a physical foaming agent is immersed between graphite layers under the action of high pressure, the foaming agent cracks between the graphite layers under the heating condition, and ultrasonic cavitation stripping is carried out in a continuous ultrasonic device, so that the graphene is prepared by continuous ultrasonic stripping. The method not only improves the yield of the graphene, but also is suitable for large-scale continuous production. However, the graphene obtained by the method has uneven thickness and poor integrity, and has the defect that the graphene is difficult to purify and separate, so that the quality of the graphene product is reduced. Chinese patent publication No. CN108975321A discloses a method for preparing graphene by hydrodynamic cavitation liquid-phase exfoliation, which comprises dispersing graphite in a solvent containing a surfactant to obtain a graphite dispersion, feeding into a cavitation element, controlling certain cavitation parameters, and freeze-drying to obtain graphene powder. The method has the advantages of simple operation, high stripping efficiency, low energy consumption, no environmental pollution and easy large-scale production. However, the method directly disperses graphite in a solvent containing a surfactant, and as the graphite layers have small spacing (only 0.334 nm) and large surface tension (40-43 mN/m), the dispersing agent cannot be fully immersed between the graphite layers due to direct addition without treatment, the final product graphene partially overlaps (overlapping between sheets) or agglomerates (aggregation between particles) inevitably occurs, the quality of the graphene is influenced, the dispersing agent is added, the dispersing agent needs to be removed at the later stage, but the removing effect is not ideal, the dispersing agent is difficult to completely remove, the dispersing agent is attached to the surface of the graphene and is an inert substance, and the performances and the application of the subsequent graphene such as electric conduction and heat conduction are influenced.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide the method for preparing the graphene, which has the advantages of simple steps, high production efficiency, low production cost, complete structure of the obtained graphene, few layers, no overlapping, no agglomeration and less defects.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method of preparing graphene, characterized by: heating expandable graphite in a graphite expansion furnace to 850-900 ℃, expanding to obtain expanded graphite with gaps of 0.7-0.8nm, wherein the expanded graphite contains functional groups containing hydroxyl and carboxyl with oxygen content of 2-3%, dispersing the obtained expanded graphite in a strong polar solvent to obtain a graphite interlayer compound, and performing circulating cavitation by using a cavitation device to obtain graphene slurry.
The multiplying power of the expandable graphite is 100mL/g-700mL/g, preferably 300mL/g-500 mL/g; purity 90% -99.99%, preferably purity 95% -99.9%; the particle size is 50-1200 meshes, the preferred particle size is 80-325 meshes, and the oxygen content is 2% -5%, and the preferred particle size is 2% -3%.
The strong polar solvent is one or a mixture of more of water, ethanol, formamide, acetamide, nitrogen methyl pyrrolidone carboxylic acid and tetrahydrofuran, and preferably one or a mixture of more of water, ethanol and tetrahydrofuran.
The preferred mass ratio of the expanded graphite of the present invention in the strongly polar solvent is 1% to 6%.
The cavitation device is a liquid jet cavitation machine, an orifice plate cavitation machine, a vortex cavity cavitation machine or a vortex cavitation machine.
The circulating cavitation technological parameters of the cavitation device are as follows: the output pressure of the high-pressure pump is 30-80MPa, the cavitation collapse temperature is 1000-.
The graphene slurry is formed by volatilizing a graphene material output by a cavitation device, and the resistivity of the graphene slurry is between 0.004 and 0.015 omega cm.
The graphene obtained by adopting the preparation steps has the advantages of simple steps, high production efficiency, low production cost, complete structure of the obtained graphene, few layers, no overlapping, no agglomeration, few defects and the like.
Detailed Description
The invention is further illustrated below:
a method for preparing graphene is characterized by comprising the following steps: heating expandable graphite in a graphite expansion furnace to 850-900 ℃, expanding to obtain expanded graphite with gaps of 0.7-0.8nm, wherein the expanded graphite contains hydroxyl and carboxyl functional groups with oxygen content of 2-3%, dispersing the obtained expanded graphite in a strong polar solvent to obtain a graphite interlayer compound, and circularly cavitating by using a cavitation device to obtain graphene slurry, wherein the multiplying power of the expandable graphite is 100-700 mL/g, preferably 300-500 mL/g; purity is 90% -99.99%, preferably purity is 95% -99.9%; the particle size is 50-1200 meshes, the preferred particle size is 80-325 meshes, the oxygen content is 2-5%, the preferred particle size is 2-3%, the strong polar solvent is one or a mixture of more of water, ethanol, formamide, acetamide, N-methyl pyrrolidone carboxylic acid and tetrahydrofuran, the preferred mass ratio of the expanded graphite in the strong polar solvent is 1-6%, the cavitation device is a liquid jet cavitation machine or an orifice plate cavitation machine or a vortex cavity cavitation machine or a vortex cavitation machine, and the circulating cavitation technological parameters of the cavitation device are as follows: the output pressure of the high-pressure pump is 30-80MPa, the cavitation collapse temperature is 1000-2000K, the flow velocity of the material jet relative to the inner wall of the cavitation cavity is more than 125m/S, the cavitation time is more than 50 microseconds, the graphene slurry is formed by volatilizing the graphene material output by the cavitation device, and the resistivity is 0.004-0.015 omega cm.
Has the advantages that: compared with the prior art for preparing graphene, the method for preparing the graphene material by taking the expandable graphite as the raw material through stripping has the following characteristics:
1. the invention provides a method for preparing graphene by using expandable graphite as a raw material and preparing the expandable graphite through high-temperature treatment, wherein the expandable graphite has the advantages that an intercalator is inserted into a graphite sheet layer, the intercalator is volatilized by using high temperature, and the graphite sheet layer is opened.
2. The surface of the expanded graphite prepared by the method is provided with certain hydroxyl and carboxyl functional groups, so that the expanded graphite can be directly dispersed in a strong polar solvent without adding a dispersing agent in subsequent treatment, the influence on the conductivity of a final product is small, and the subsequent application of graphene is ensured.
3. According to the invention, a strong polar solvent and a cavitation device are combined, and the graphene is subjected to multiple cavitation stripping, so that the graphene is subjected to graded mixing stripping, and the prepared graphene is more uniform in size.
4. The method is simple, large-scale continuous production can be realized, the graphene prepared by the method can be used for screening and preparing graphene powder with different layer specifications according to the requirements of the demand field, the preparation process is simple, the production cost is greatly and effectively reduced, the guarantee is provided for large-scale application of the graphene, no pollutant is generated in the preparation process, the method is green and environment-friendly, and no pollution is caused to the environment.
5. The invention does not adopt a dispersing agent, does not need to be removed in the later period, does not adhere to the surface of a finished product, does not form an inert position, and has the advantages of simple process operation, good stability, high safety, environmental protection, no toxicity, low price, small influence on the electric and heat conducting properties, convenient subsequent use, wider application range and the like.
Example 1
(1) Expandable graphite is put in a special expanded graphite furnace at the high temperature of 850-900 ℃ to obtain vermicular expanded graphite with the gap of 0.7nm, and expanded graphite powder with the expansion multiplying power of 400mL/g, the purity of 99.5 percent, the grain sizes of 100 meshes and 150 meshes and the oxygen content of 2 percent is screened for standby.
(2) Accurately weighing 40 kg of 5 percent ethanol aqueous solution, pouring the ethanol aqueous solution into a first stirring tank, adding 1000 kg of deionized water into the first stirring tank, and uniformly stirring to form the mixed polar solvent. Then 35 kg of the prepared expanded graphite powder was accurately weighed and added to the second stirring tank, and stirred at high speed for 3 hours. Then adding the graphite powder which is uniformly stirred into the first stirring tank, continuously stirring for 30 minutes to form a uniform mixed material, transferring the mixed material into a feeding tank, and continuously stirring to prevent the mixed material from standing for a long time to cause precipitation.
(3) The mixed material is input into a high-pressure pump cavity of a liquid jet cavitation machine from a feeding tank by a delivery pump, and then is injected into a cavitation device by the high-pressure pump for cavitation, the output pressure of the high-pressure pump is controlled to be 30-40MPa, the cavitation collapse temperature is more than 1000K, the flow velocity of the material jet relative to the inner wall of the cavitation cavity is more than 125m/S, the cavitation time is more than 90 microseconds, the material subjected to cavitation stripping is circulated for 3 times, the material subjected to cavitation stripping is cooled after each cavitation stripping, so that the temperature of the material in the cavitation process is stable, and the total cavitation time is controlled to be more than 2 hours. In the process, mutual pollution of the cavitated materials and the non-cavitated physicochemical materials is avoided. And a pressure control valve connected to a cavitation cavity of the cavitator automatically opens and outputs the liquid-solid mixed graphene material, and the liquid graphene slurry is formed through volatilization. The detection shows that the grain size sheet diameter D90 is less than or equal to 8.5 μm, and the resistivity reaches 0.006 omega cm.
Example 2
(1) Expandable graphite is put in a special expanded graphite furnace at the temperature of 850-900 ℃ to obtain vermicular expanded graphite with the gap of 0.8nm, and expanded graphite powder with the expansion multiplying power of 450mL/g, the purity of 99.5 percent, the grain size of 180 meshes and 200 meshes and the oxygen content of 2 percent is screened for later use.
(2) Accurately weighing 40 kg of 5 percent ethanol aqueous solution, pouring the 40 kg of 5 percent ethanol aqueous solution into a first stirring tank, adding 1000 kg of deionized water into the first stirring tank, and uniformly stirring to form the mixed polar solvent. Then 20 kg of the prepared expanded graphite powder is accurately weighed and added into a second stirring tank, and the mixture is stirred at a high speed for 3 hours. Then adding the graphite powder which is uniformly stirred into the first stirring tank, continuously stirring for 30 minutes to form a uniform mixed material, transferring the mixed material into a feeding tank, and continuously stirring to prevent the mixed material from standing for a long time to cause precipitation.
(3) The mixed material is input into a pump cavity of a high-pressure pump of a liquid jet cavitation machine by a delivery pump, the mixed material is injected into a cavitation device by the high-pressure pump for cavitation, the output pressure of the high-pressure pump is controlled to be 40-45MPa, the cavitation collapse temperature is more than 1000K, the flow velocity of the material jet relative to the inner wall of the cavitation cavity is more than 125m/S, the cavitation time is more than 90 microseconds, the material to be subjected to circular cavitation stripping is carried out for 3 times, the material to be subjected to cavitation stripping is cooled after each cavitation stripping, the temperature of the material in the cavitation process is stable, and the total cavitation time is controlled to be more than 2 hours. In the process, mutual pollution of the cavitated materials and the non-cavitated physicochemical materials is avoided. And a pressure control valve connected to a cavitation cavity of the cavitator automatically opens and outputs the liquid-solid mixed graphene material, and the liquid graphene slurry is formed through volatilization. The detection shows that the particle size D90 is less than or equal to 10 mu m and the conductivity is 0.009 omega cm.
Example 3
(1) Expandable graphite is put in a special expanded graphite furnace at the temperature of 850-900 ℃ to obtain vermicular expanded graphite with the gap of 0.75nm, and expanded graphite powder with the expansion multiplying power of 450mL/g, the purity of 99.6 percent, the grain diameter of 150 meshes and the oxygen content of 2.3 percent is screened for later use.
(2) 40 kg of deionized water is accurately weighed and poured into a first stirring tank, 1000 kg of deionized water is added into the first stirring tank, and the materials are mixed to form the polar solvent. And then accurately weighing 20 kilograms of prepared expanded graphite powder, adding the expanded graphite powder into a second stirring tank, stirring at a high speed for 3 hours, then adding the uniformly stirred graphite powder into the first stirring tank, continuously stirring for 30 minutes to form a uniform mixed material, transferring the mixed material into a feeding tank, continuously stirring, and preventing the mixed material from standing for a long time to cause precipitation.
(3) The mixed material is input into a high-pressure pump cavity of a liquid cavitation machine by a delivery pump, and then is injected into a cavitation device by the high-pressure pump for cavitation, the output pressure of the high-pressure pump is controlled to be 80MPa, the cavitation collapse temperature is more than 1500K, the flow velocity of the material jet relative to the inner wall of the cavitation cavity is more than 130m/S, the cavitation time is more than 90 microseconds, the material to be subjected to cavitation stripping is circularly cavitated for 4 times, the material to be subjected to cavitation stripping is cooled after each cavitation stripping so as to ensure the temperature stability of the material in the cavitation process, and the total cavitation time is controlled to be more than 2 hours. In the process, mutual pollution of the cavitated materials and the non-cavitated physicochemical materials is avoided. And a pressure control valve connected to a cavitation cavity of the cavitator automatically opens and outputs the liquid-solid mixed graphene material, the graphene material is volatilized to form liquid graphene slurry, and the liquid graphene slurry is dried to obtain graphene powder. The detection shows that the granularity D90 is less than or equal to 9 mu m and the conductivity is 0.006 omega cm.
Example 4
(1) Expandable graphite is put in a special expanded graphite furnace at the high temperature of 850-900 ℃ to obtain vermicular expanded graphite with the gap of 0.72nm, and expanded graphite powder with the expansion multiplying power of 500mL/g, the purity of 99.7 percent, the grain diameter of 150 meshes and the oxygen content of 2 percent is screened for later use.
(2) 50 kg of a mixture of 5% ethanol water is accurately weighed and poured into a first stirring tank, then 100 kg of a mixture of nitrogen methyl pyrrolidone carboxylic acid and 900 kg of deionized water is added into the first stirring tank, and the mixture is uniformly stirred to form a mixed polar solvent. And accurately weighing 35 kg of prepared expanded graphite, adding the expanded graphite into a second stirring tank, stirring at a high speed for 3 hours, adding the uniformly stirred graphite powder into the first stirring tank, continuously stirring for 30 minutes to form a uniform mixed material, transferring the mixed material into a feeding tank, continuously stirring, and preventing the mixed material from standing for a long time to cause precipitation.
(3) The mixed material is input into a high-pressure pump cavity of a liquid cavitation machine by a delivery pump, the mixed material is injected into a cavitation device by the high-pressure pump for cavitation, the output pressure of the high-pressure pump is controlled to be 80MPa, the cavitation collapse temperature is more than 1500K, the flow velocity of the material jet relative to the inner wall of a cavitation cavity is more than 130m/S, the cavitation time is more than 90 microseconds, the material to be cavitated and stripped is cooled for 4 times, the material to be cavitated and stripped is cooled after each cavitation stripping, so that the temperature of the material in the cavitation process is stable, and the total cavitation time is controlled to be more than 2 hours. In the process, mutual pollution of the cavitated materials and the non-cavitated physicochemical materials is avoided. And a pressure control valve connected to a cavitation cavity of the cavitator automatically opens and outputs the liquid-solid mixed graphene material, and the liquid graphene slurry is formed through volatilization. The detection shows that the particle size D90 is less than or equal to 8 mu m, and the conductivity is 0.005 omega cm.
Example 5
(1) Expandable graphite is put in a special expanded graphite furnace at the high temperature of 850-900 ℃ to obtain vermicular expanded graphite with the gap of 0.76nm, and expanded graphite powder with the expansion multiplying power of 500mL/g, the purity of 99.7 percent, the grain diameter of 200 meshes and the oxygen content of 3 percent is screened for later use.
(2) Accurately weighing 40 kg of a mixture containing 10% of ethanol water, pouring the mixture into a first stirring tank, adding 50 kg of a mixture of tetrahydrofuran and 950 kg of 10% of ethanol water into the first stirring tank, and uniformly stirring to form a mixed polar solvent. And then accurately weighing 30 kilograms of prepared expanded graphite, adding the expanded graphite into a second stirring tank, stirring at a high speed for 3 hours, then adding the uniformly stirred graphite powder into the first stirring tank, continuously stirring for 30 minutes to form a uniform mixed material, transferring the mixed material into a feeding tank, continuously stirring, and preventing the mixed material from standing for a long time to cause precipitation.
(3) The mixed material is input into a high-pressure pump cavity of a liquid cavitation machine by a delivery pump, the mixed material is injected into a cavitation device by the high-pressure pump for cavitation, the output pressure of the high-pressure pump is controlled to be 80MPa, the cavitation collapse temperature is more than 1500K, the flow velocity of the material jet relative to the inner wall of the cavitation cavity is more than 150m/S, the cavitation time is more than 90 microseconds, the material to be subjected to circular cavitation stripping is subjected to 5 times of circulation cavitation stripping, the material to be subjected to cavitation stripping is cooled after each time of cavitation stripping, so that the temperature stability of the material in the cavitation process is ensured, and the total cavitation time is controlled to be more than 2.5 hours. In the process, mutual pollution of the cavitated materials and the non-cavitated physicochemical materials is avoided. And a pressure control valve connected to a cavitation cavity of the cavitator automatically opens and outputs the liquid-solid mixed graphene material, the graphene material is volatilized to form liquid graphene slurry, and the liquid graphene slurry is dried to obtain graphene powder. The detection shows that the particle size D90 is less than or equal to 4 mu m and the conductivity is 0.005 omega cm.
Example 6
(1) Expandable graphite is put in a special expanded graphite furnace at the high temperature of 850-900 ℃ to obtain vermicular expanded graphite with the gap of 0.77nm, and expanded graphite powder with the expansion multiplying power of 450mL/g, the purity of 99.8 percent, the grain diameter of 150 meshes and the oxygen content of 2.5 percent is screened for standby.
(2) Accurately weighing 50 kg of formamide, pouring the formamide into a first stirring tank, adding a mixture of 50 kg of ethanol and 950 kg of formamide into the first stirring tank, and uniformly stirring to form a mixed polar solvent. And accurately weighing 40 kg of prepared expanded graphite, adding the expanded graphite into a second stirring tank, stirring at a high speed for 3 hours, adding the uniformly stirred graphite powder into the first stirring tank, continuously stirring for 30 minutes to form a uniform mixed material, transferring the mixed material into a feeding tank, continuously stirring, and preventing the mixed material from standing for a long time to cause precipitation.
(3) Inputting the mixed material into a cavity of a high-pressure pump of a liquid vortex cavitation machine by using a delivery pump, injecting the mixed material into a cavitation device by using the high-pressure pump for cavitation, controlling the cavitation pressure to be 70MPa, controlling the cavitation collapse temperature to be more than 1200K, controlling the flow rate of the material jet relative to the inner wall of the cavitation cavity to be more than 125m/S, controlling the cavitation time to be more than 90 microseconds, carrying out circulating cavitation stripping for 4 times, cooling the material to be subjected to cavitation stripping after each cavitation stripping so as to ensure the temperature stability of the material in the cavitation process, and controlling the total cavitation time to be more than 2 hours. In the process, mutual pollution of the cavitated materials and the non-cavitated physical and chemical materials is avoided. And a pressure control valve connected to a cavitation cavity of the cavitator automatically opens and outputs the liquid-solid mixed graphene material, and the liquid graphene slurry is formed through volatilization. Through detection, the particle size D90 is less than or equal to 4 mu m, and the conductivity is 0.004 omega cm.
In conclusion, the total oxygen content of the hydroxyl and carboxyl functional groups in the expanded graphite is about 2.3%, so that the subsequent full infiltration with a solvent can be ensured, the use of a dispersing agent is omitted, and the electric and heat conducting performance of a final product is not influenced.
While the method and process flow of the present invention has been described in connection with preferred embodiments, the invention is not intended to be limited to the specific form set forth herein, but rather, to the subcombination of the various elements which are within the scope of the invention as defined by the claims are intended to be covered thereby.
Claims (2)
1. A method of preparing graphene, characterized by: heating expandable graphite in a graphite expansion furnace to 850-900 ℃, expanding to obtain expanded graphite with gaps of 0.7-0.8nm, wherein the expanded graphite contains functional groups containing hydroxyl and carboxyl with oxygen content of 2-3%, dispersing the obtained expanded graphite in a strong polar solvent to obtain a graphite interlayer compound, and circularly cavitating by using a cavitation device to obtain graphene slurry, wherein the multiplying power of the expandable graphite is 100-700 mL/g, and the purity of the expandable graphite is 90-99.99%; the particle size is 50-1200 meshes, the oxygen content is 2-5%, the mass ratio of the expanded graphite in the strong polar solvent is 1-6%, the cavitation device is a liquid jet cavitation machine, a pore plate cavitation machine, a vortex cavity cavitation machine or a vortex cavitation machine, and the circulating cavitation technological parameters of the cavitation device are as follows: the output pressure of the high-pressure pump is 30-80MPa, the cavitation collapse temperature is 1000-2000K, the flow velocity of the material jet relative to the inner wall of the cavitation cavity is more than 125m/S, the cavitation time is more than 50 microseconds, the graphene slurry is formed by volatilizing the graphene material output by the cavitation device, and the resistivity is 0.004-0.015 omega cm.
2. The method according to claim 1, wherein the strongly polar solvent is one or more selected from water, ethanol, formamide, acetamide, nitrogen methyl pyrrolidone carboxylic acid, and tetrahydrofuran.
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| CN113697801B (en) * | 2021-10-15 | 2022-10-25 | 黑龙江省科学院高技术研究院 | Graphene preparation method based on vortex cavitation technology |
| CN115093666B (en) * | 2022-06-21 | 2023-08-15 | 东莞市伟杰顺华触控技术有限公司 | Polymer conductive composite material for temperature and stress sensor and preparation method thereof |
| CN115536016A (en) * | 2022-10-12 | 2022-12-30 | 三门峡芳瑞杜仲产业技术研究院有限公司 | Physical graphene stripping method |
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